Processes for breaking petroleum emulsions



Patented Oct. 10, 1950 2,524,892 PROCESSES FOR BREAKING PETROLEUM EMULSIONS Melvin De Groote, University City, and Bernhard Keiser, Webster Groves, Mo., assignors to Petrolite Corporation, Ltd., Wilmington, Del., a corporation of Delaware No Drawing. Application June 26, 1948, Serial No. 35,529

Claims. 1

This invention relates to processes or procedures particularly adapted for preventing, breaking, or resolving emulsions of the water-inoil type, and particularly petroleum emulsions. This application is, in part, a continuation of our co-pending application Serial No. 666,825, filed May 2, 1946, now abandoned.

Complementary to the above aspect of our invention is our companion invention concerned with the new chemical products or compounds used as the demulsifying agents in said aforementioned processes or procedures, as well as the application of such chemical compounds, products and the like, in various other arts and industries, along with the method for manufacturing said new chemical products or compounds which are of outstanding value in demulsification. See our co-pending application Serial No. 35,530, filed June 26, 1948, which, in turn, is a continuation of our co-pending application Serial No. 758,492, filed July 1, 1947, now abandoned.

1 Our invention provides an economical and rapid process for resolving petroleum emulsions of the water-in-oil type, that are common y referred to as cut oil, roily oil, emulsified oil, etc., and which comprise fine droplets of naturally-occurring waters or brines dispersed in a more or less permanent state throughout the oil which constitutes the continuous phase of the emulsion.

It also provides an economical and rapid process for separating emulsions which have been prepared under controlled conditions from mineral oil, such as crude oil and relatively soft waters or weak brines. Controlled emulsification and subsequent demulsification, under the conditions just mentioned, are of significant value in removing impurities, particularly inorganic salts, from pipeline oil.

Demulsification, as contemplated in the present application, includes the preventive step of commingling the demulsifier with the aqueous component which would or might subsequently become either phase of the emulsion, in the absence of such precautionary measure. Similarly, such demulsifier may be mixed with the hydrocarbon component. Reference is made to our co-pending applications Serial No. 8,722 and Serial No. 8,723, both filed February 16, 1948, now Patents Nos. 2,499,365 and 2,499,366, respectively, both dated March '7, 1950.

For sake of convenience and in order to indicate with clarity the relationship between the compounds herein employed as demulsifying agents in relation to other compounds employed for the same purpose and described in our last two mentioned co-pending applications, to wit, Serial Nos. 8,722 and 8,723, reference is made to still another of our co-pending applications, to wit, Serial No. 8,731, also filed February 16, 1948 (now abandoned). In this last mentioned copending application we have stated as follows:

We have found that if solvent-soluble resins are prepared from difunctional (direactive) phenols in which one of the reactive (0 or p) positions of the phenol is substituted by a hydrocarbon radical having 4 to 8 carbon atoms, in the substantial absence of trifunctional phenols, and aldehydes having not over 8 carbon atoms, subsequent oxyalkylation, and specifically oxyethylation, yields products of unusual value for demulsification purposes, provided oxyalkylation is continued to the degree that hydrophile properties are imparted to the compound. By substantial absence of trifunctional phenols we mean that such materials may be present only in amounts so small that they,do,not interfere with the formation of a solventr-soluble resin product, and, especially, of a hydrophile oxyalkylated derivative thereof. The actual amounts to be tolerated will, of course, vary with the nature of the other components of the system, but in general, the proportion of trifunctional phenols which is tolerable in the conventional resinification procedures illustrated herein is quite small. In experiments following conventional procedure, using an acid catalyst in which we have included trifunctional phenols in amounts of from 3% to about 1% or somewhat less, based on the difunc-' tional phenols, we have encountered difiiculties in preparing oxyalkylated derivatives of the type useful in the practice of this invention.

Such products are rarely a single chemical compound, but are almost invariably a mixture of cogeners. One useful type of compound may be exemplified in an idealized simplification in the following formula:

- fusible, organic solvent-soluble resin polymer on on G H H R n" R In these formulae n" represents a numeral varying from 1 to 13, or even more, provided the parent resin is fusible and organic solvent-soluble; n represents a numeral Varying from 1 to The demulsi fying agents employed the present process are similar to those described in our last aforementioned co-pending application, to wit, Serial No. 8,731, and are also obtained from solvent-soluble, fusible, phenol-aldehyde resins. The specific demulsifying agents herein specified are derived from phenols having a long chain meta substituent in combination with both 'difunctional and trifunctional phenols. Thus, in the simplest aspect in which oxyalkylated solvent-soluble, fusible resins are derived solely from a long chain meta-substituted phenol, such as anacardol, dihydroanacardol, tetrahydroanacardol, side chain chlorinated cardanol, etc., the compound may be exe mplified in ,an idealized simplification in the following formula:

O(Cfl4O)n'H O(C'zH O),uH ()(CAHAO)1\'H which, in turn, is considered a "derivative of the fusible, organic solvent-soluble, resin polymer OH .,OH.,. on

In these formulae 1t"l 'rei fe'sents a numeral varying from 1 to 13, fr even more, provided the parent resin is fusible aha organic solventsoluble; n represents a numeral varying from 1 to 20, with the provisdthatthe'averag value of n be at least 2; and is a'hydrocarbon radical or a chlorinated hydrocarbon radical having carbon atoms and derived fromasliew nutshell liquid with or without hydrogenationl Th'cse numerical Values of n and n"-"afe, of"cours', on a statistical basis. Bearing in mind that in-the instant invention the 'oxyalkylated resin is derived from a mixture of p'henols, it becomes obvious that the structural for'mula is 'a mixture between the limit aboveindicateld and also a comparable structure related to resins, which, while fusible and solvent-soluble, are derived solely from trifunctional phenols. Such resins are illustrated by resoles and Novolak'si. Howeverfin light of the generally understood difficulties of icharacterizing such resins, and particularly in light of the variety of catalysts which can be used, no effort is being made in the instant'case to present such other directional limit. I

The present invention involves the use as a demulsifier of a hydrophile oxyalk'ylated organic solvent-soluble, fusible phenol-aldehyde resin derived from an aldehyde having not more than 8 carbon atoms and a cashew nutshell liquid or a hydrogenated or chlorinated derivative thereof, in combination with trifunctional phenols having not over 24 carbon atoms inthe substituent radical. Such oxyalkylated phenol-aldehyde resins owe their hydrophil eproperty to the fact that the ratio of oxyalkylateid groups to phenolic nuclei is at least 2 to l, and with the further limitation that the alkylene radicals of the oxyalkylene groups are ethylene, propylene, butylene, hydroxypropylene, or hydroxybutylene, corresponding to the alpha-beta alkylene oxide, ethylene oxides, alpha-beta propylene oxides, alpha-beta butylene oxides, glycide or methylglycide.

More particularly, the present invention involves the use, as a demulsifier, of compounds having the following characteristics:

(1) Essentially a polymer, probably linear 4 but not necessarily so, hating fat least '3, and preferably, not over 15 or 20ph'enolic or structural units. It may have more, as previously noted.

-(2) The parent resin polymer, being fusible and organic solvent-soluble, as hereinafter described.

(3) The parent resin polymer, being free from cross-linking, or structure which cross-links during the heating incident to the oxyalkylation procedure to an extent sufficient to prevent the possession of hydrophile or sub-surface-active or surface-active properties by the oxyalkylated resin. Minor proportions of trifunctional phenols sometimes present in commercial difunctional phenols, are usually harmless.

(4) Each alkyleneoxy group is introduced at the phenolic hydroxyl position, except possibly in an exceptional instance, where a stable m'ethylol group has been formed by virtue of resin manufacture, in presence of an alkaline catalyst. Such occurrence of a stable methylol radical is the exception, rather than the rule, and in any event, apparently does not occur when the resin is manufactured in the presence of an acid catalyst.

5) The total number or alkyleneoxy radicals: introduced must be least equal twice the of sub-surface active and 'surfaceactive compounds.

(7) The use of a product derived fromcashew nutshell liquid with or without hydrogenation,

so that at least a significant proportion of the phenolic nuclei containa meta-substituted hydrocarbon side chain having 15 carbon atoms.

We have found that the remarkableproperties of the parent materials as demulsifiers persist in derivatives which bear a simple genetic relationship to the parent materiaL'and infact, to the ultimate resin polymer, for instance, in the products obtained by reaction of the oxyalkylated compounds with low molal 'monocarboxy acids, high molal monocarbox'y acids, polyoarboxy acids or their anhydrides, alpha-chloro monocarboxy acids, epiohlorohydrin, etc. The derivatives also preferably must be obtained from oxyalkylated products, showing at least the necessary hydrophile properties, terse.

More specifically "then, the new compounds herein'described, and particularly for'use as demulsifying agents, are obtained from cashew nutshell liquid, anacardol (3 penta decadienylphenol), cardanol (dihydro'anacardol or 3-pentadecenylphenol), andhydrog'e'nated cardanol (dihydrocardanol or tetrahydroanacardol'or 3-penta-decylphenol), in combination with both difunctional and trifunctional phenols, as previously specified and illustrated by subsequent examples.

The new compounds or compositions herein described are prepared, in part, from the phenolic compositions present in or derived from the oils extracted from the Anacardium genus of the Anacardiaceae family. Cashew nutshell liquid is COOH isHn Pyrolytic distillation causes conversion into phenols.

Another derivative of cashew nutshell liquid, in addition to the hydrogenated derivative, is the chlorinated anacardol and chlorinated cardanol. For practical purposes, the principal constituent of chlorinated cashew nutshell liquid is chlorinated cardanol. Chlorination refers to side chain chlorination only and not to nuclear chlorination. The actual purpose of chlorination is well known and involves the addition of approximately 25% of chlorine, by weight, so as to saturate any ethylene linkage. See U. S. Patent No. 2,399,735, dated May 7, 1946, to Harvey.

These reactive phenolic compounds are combined with suitable aldehydes, including formaldehyde and its isomers, acetaldehyde and higher aldehydes, such as butyraldehyde, heptaldehyde, cyclic aldehydes, such as benzaldehyde, furfural, etc. Resins can be prepared in which part of the treated cashew nutshell liquid or its derivatives is replaced by another trifunctional phenol, such as ordinary phenol (hydroxy benzene) metacresol, or similar derivatives, in which the ethyl or propyl group appears in the meta position.

' As previously stated, these anacardic acid phenols are herein employed in' combination with both a trifunctional phenol and a difunctional phenol, such as ortho cresol, paracresol, parapropylphenol, para-butylphenol, para-amylphenol, para hexylphenol, para isooctylphenol, ortho-phenylphenol, ortho-benzylphenol, parabenzylphenol, para cyclohexylphenol, phenylphenylolmethyl-methane, etc. The effectiveness of the chemical compounds herein contemplated for numerous purposes, appears to be, in a large measure, directly related to the long carbon atom chain of the anacardic acid phenol in a polymer interrupted by phenols having other structures. For instance, we have prepared excellent products in which one mole of cardanol or its equivalent, such as hydrogenated cardanol, has been combined with 2, 3 or 4 moles of orthocresol, tertiary amylphenol, tertiary butylphenol, etc., or other similar difunctional phenols, along with a single mole of metacresol or phenol. The various combinations are illustrated by subsequent examples, and, in any event, there is present all three types of phenols in the phenolic reactant and at least one mole in is an anacardic acid phenol.

- -Any aldehyde capable of forming a methylol or a substituted methylol group and having not more than 8 carbon atoms is satisfactory, so long as it does not possess some other functional group or structure which will conflict with the resinification reaction or with the subsequent oxyalkylation of the resin, but the use of formaldehyde, in its cheapest form of an aqueous solution, for the production of the resins, is particularly advantageous. Solid polymers of formaldehyde are more expensive and higher aldehydes are both less reactive, and are more expensive. Furthermore, the higher aldehydes may undergo other reactions which are not desirable, thus introducing difiiculties into the resinificationstep. Thus, acetaldehyde, for example, may

6 undergoan aldol condensation, and it and most of the higher aldehydes enter into self-resinification when-treated with strong acids or alkalies. On the other hand, higher aldehydes frequently beneficially affect the solubility and fusibility of a resin. This is illustrated, for example, by the different characteristics of the resin prepared from para-tertiary amylphenol and formaldehyde, on one hand, and a comparable product.

prepared from the same phenolic reactant and heptaldehyde, on the other. hand.. The former, as shown in certain subsequent examples, is a hard, brittle, solid, whereas, the latter is soft and tacky and obviously easier to handle in the subsequent oxyalkylation procedure.

Cyclic aldehydes may be employed, particularly benzaldehyde.

The employment of furfural requires careful control, for the reason that, in addition to its aldehydic function, furfural can form vinyl condensations by'virtue of its unsaturated structure. The production of resins from furfural for use in preparing products for the present process is most conveniently conducted with weak alkaline catalysts and often with alkali metal carbonates. Useful aldehydes, in addition to formaldehyde, are acetaldehyde, propionic aldehyde, butyraldehyde, z-ethylhexanol, ethyl-butyraldehyde, heptaldehyde and benzaldehyde, furfural and glyoxal. It would appear that the use of glyoxal should be avoided, due to the fact that it is tetrafunctional. However,'our experience has been that, in resin'maniifacture and particularly as described herein, apparently only one of the aldehydic 'functions enters into the resinification reaction. The inability of the other aldehydic function to enter into the reaction is presumably due to steric hindrance. Needless to say, one can use a mixture of two or more aldehydes, although usually thishas no advantage.

Resins of the kind which are used as intermediates for the compounds used in the practice of this invention are obtained with the use of acid catalysts or alkaline catalysts, or without the use of any catalyst at all. Among the useful alkaline catalysts are ammonia, amines and quaternary ammonium bases. It is generally accepted that when ammonia and amines are employed as catalysts, they enter into the condensation reaction, and in fact, m'ay operate by initial combination with the aldehydic reactant. The compound hexamethylenetetramine, illustrates such a combination. In light of these various reactions, it becomes difiicult to present any formula which would depict the structure of the variousresins prior to oxyalkylation. More will be said subsequently as to the difference between the use of alkaline catalyst and an acid catalyst; even in the use of an alkaline catalyst there is considerable evidence to indicate that the products are not identical where difierent basic materials are employed. The basic materials employed include not only those previously enumerated, but also the hydroxides of the alkali metals, hydroxides of the alkaline earth metals, salts of strong bases and weak acids, such as sodium acetate, etc.

Previous reference has been made to suitable trifunctional phenols. These either have no side chain or a short side chain, such as metacresol, and excluding any trifunctional phenols having 4 carbon atoms or more in the meta position substituent.

It has been pointed out previously that the resins employed as raw materials in the manu- 7? facture of :th'e;.herein idescribexi' compounds; areobtained fromanacardic acid phenolsalone, or. in combination with difunctional phenols or functional phenols, or-both. Nodescription of, trlfunctional phenols is needed; and asto. difunctional phenols, reference is made to. the. language usedin our. aforementioned: covpend. ing applications Serial Nos- 8,722. and 8,723, both filed February 16, 1948. As to anacardic acid; phenols, asherein described, one may convene iently employ the formula.

in which R represents a hydrocarbon radical or a chlorinated hydrocarbon radical, as. exemplified by cashew nutshell liquid phenol, or its hydrogenated or chlorinated derivative.

' The manufacture of organic solvent-soluble thermoplastic phenol-aldehyde resins is concerned-largely with the manufacture of:

(0.) Resoles or Novolaks from trifunctiona phenols;

(b) Manufacture of varnish resins from difunctional phenols; and

(c) The manufacture of the cardanolv type resin from phenols or phenolic mixtures, as previously specified.

There is an ample-descriptionin theliterature as to the manufacture. of. resins fromcardanol type phenols alone and in combination with other phenols. Anysuitable-process-may be employed to makethe-herein described resinswhich are used as raw materials. Wehave found it most convenient to use thesame general procedures which are applicable to the manufacture ofresins from d-ifunctional phenols, particularly in which the substituent radical has 4' to 8 carbon atoms. Thisprocedure is described, for example, in'the literature and specific examples included in our aforementioned co-pendingapplication Serial No. 8,731, fi1ed February 16, 1948.

Thermoplastic or fusible phenol-aldehyde resins are usually manufactured for the varnish tradeand. oil solubility isof prime importance. For this-reason, the common reactants employed are butylatedphenols, amylated phenols, phenylphenols, etc. The methods employed in manufacturing such resins are similar to those employed in the manufacture of ordinary phenolformaldehyde resins, that either anacidor alkaline catalyst is usually employed. The procedure usually differs from that'employed; in the manufacture of ordinary phenol-aldehyde'resins, in that phenol, being water-soluble, reacts readily with an aqueous aldehyde solution; without further difficulty, while when a water insoluble phenol is employed, some modificationis usually a opted to increase the interfacialsurface, and thus. cause reaction to take place. A common solvent is sometimes employed. Another procedure employs rather severe agitation to create a large interfacial area. Once the reaction starts to a moderate degree, it is possible that both reactants are somewhat soluble in the partially reacted, mass and assist in hastening the reaction.

We have found it desirable to employ a small proportion of an organic sulfo-acid as acatalyst, eitheralone oralong with a mineral acid: like sulfuric or hydrochloric acid. For example, alkylated aromatic sulfonic acids are eifectively employed; Since commercial forms-of such acids are commonlyl-theiralkali salts, it is sometimes.

scribedindeta-il. Another variation of procedure istoemploy such organic sulfo-acids, in the form oftheir salts, in connection with an alkali-catalyzed resinification procedure. Detailed examples are included subsequently.

Sometimes conventional resinification procedure is employed, using either acid or alkaline: catalysts to produce low-stage resins. Such resin may be employed as such, or may be altered or converted into-high-stage resins, or in any event, into. resins of higher molecular weight, by heating along; withtheemploymentof vacuum so as tosplit off-water or formaldehyde, or both. Generally speaking-temperature employed, particularly with vacuum, may be in the neighborhoodiof -to,250-" 6., or thereabouts. I

In the-hereto appended claims there is specified, among other things, theresin polymer con.- taining at least 3 phenolic nuclei. Such minimum molecular size is most conveniently determined, as a rule, bycryoscopic method, using benzene, or some othersuitable solvent for such resins. Asa matter of fact, using theprocedures herein described-or any conventional resinification procedure will-yield products usually having definitely in excess of three nuclei- In other words, a resin having an average of 4, 5. or 5 nuclei per unitis apt to be formed as a minimum in resinification, except "under certain special conditions where vdimerization may occur.

However; if resins are prepared at substantially higher temperatures, substituting cymene, tetralin; etc., orv some other suitable solvent which boils or refiuxesat a higher temperature, instead of mlene, in subsequent examples, and if one doubles or triples the amount of catalyst, doubles or triples the time of refluxing, uses a marked ex cess of formaldehyde or other aldehyde, then the average size of the resin is apt to be distinctly over the above values, for example, it may average 7 to 15 units. Sometimes the expression lowstage resin or low-stage intermediate is employed-.zto mean a stage having 6 or 7 units or even less; In the appended claims we have used low-stage to mean 3 to 7 units based on average molecular weight The molecular weight determinations, of course, require. that, the product be completely soluble in the. particular solvent selected as, for instance, benzene. The molecular weight determination of such solution may involve either the freezing point as in the cryoscopic method, or, lessconvenientlyperhaps, the boiling point in an ebul-- lioscopic method. The. advantage of the ebullioscopi'c method is that, in comparison with the cryoscopic method, it is more apt to insure complete solubility. One-such common method to employ is that of Menzies and Wright (see J. Am. Chem. Soc. 43, 2309 and 2314 (1921)). Any suit able method for determining molecular weights willserve, although almost any procedure adopted has inherent limitations. A good method for determiningthe molecularweightsof resins, especially solvent-soluble resins, is the cryoscopic procedure of Krumbhaar which employs diphenylamine as a solvent (see Coating and Ink Resins, page 157, Reinhold Publishing Co. 1947) "Subsequent examples will illustrate the use of an acid catalyst, an alkaline catalyst, and no catalyst. As far as resin manufacture per se is concerned, we prefer to use an acid catalyst, and particularly a mixture of an organic sulfo-acid and a mineral acid, along with a suitable solvent, such as xylene, as hereinafter illustrated in detafl. However, we have obtained products from resins obtained by use of an alkaline catalyst which were just as satisfactory as those obtained employing acid catalysts. Sometimes a combination of both types of catalysts is used in difierent stages of resinification. Resins so obtained are also perfectly satisfactory.

In numerous instances the higher'molecular weight resins, i. e., those referred to as high-stage resins, are conveniently obtained by subjecting lower molecular weight resins to vacuum distillation and heating. Although such procedure sometimes removes only a modest amount or even perhaps no low polymer, yet it is almost certain to produce further polymerization. For instance, "acid catalyzed resins obtained in the usual manher and having a molecular weight indicating the presence of approximately 4' phenolic units or thereaboutsmay be subjected to such treatment, with the result that one obtains aresin' having approximately-double this molecular weight. 'The usual procedure is to use a secondary step, heating the resin in the presence or absence of an inert gas, including steam, or by use of vacuum.

We have found that under the usual conditions of resinification "employing phenols of the kind here described, there is little or no tendency to form binuclear compounds, i; e., dimers, resulting from the combination, for example, of 2 moles of a phenol and one mole of formaldehyde, particularly where the substituent has 4 or 5 carbon atoms. Where the number of carbon atomsin a substituent approximates the upper limit specified herein, for instance 7 or 8, there may be some tendency to dimerization. The usual procedure to obtain a dimer involves an enormousl large excess of the phenol, for instance, 8 to 10 moles per mole of aldehyde. Substituted dihydroxydiphenylmethanes obtained from substituted phenols are not resins as that term is used herein;

Although any conventional procedure ordinarily employed may be used in the manufacture of the herein contemplated resins or, for that matter, such resins may be purchased in the open market. we have found it particularly desirable to use the procedures described elsewhere herein, and. employing a combination of an organic sulfo-acid and a mineral acid as a catalyst, and xylene as a solvent. By way of illustration, certain subsequent examples are included, but it is to be understood the herein described invention is not concerned with the resins per se or with an particular method of manufacture but is concerned with the use of derivatives obtained by the subsequent oxyalkylation thereof. The phenolaldehyde resins may be prepared in any suitable manner.

Oxyalkylation, p a r t i c u l a r l y oxyethylation which is the preferred reaction, depends on contact between a non-gaseous phase and a gaseous phase. It can, for example, be carried out by melting the thermoplastic resin andsubjecting it to treatment with ethylene oxide or the like, or by treating a suitable solution or suspension.

Since the melting points o f-the ;resins are often higher than desired in theinitial stage of oxyethylation, we have found itadvantageous to use a solution or suspension of thermoplastic resin in an inert solvent such as xylene. Under such circumstances, the resin obtained in the usual manner is dissolved by heating in xylene under a reflux condenser or in any other suitable manner. Since xylene or an equivalent inert solvent is present or may be present during cxyalkylation, it is obvious there is no objection to having a solvent present during the resinifying stage if, in addition to being inert towards the resin, it is also inert towards the reactants and also inert towards water. Numerous solvents, particularly of aromatic or cyclic nature, are suitably adapted for such use. Examples of such solvents are xylene, cymene, ethyl benzene, propyl benzene, mesitylene, decalin '(decahydronaphthalene), tetralin (tetrahydronaplithalene) ethylene glycol diethylether, diethylene glycol diethylether, and tetraethylene glycol dimethylether, or mixtures of one or more; Solvents such as dichloroethylether, or dichloropropylether may be employed either alone or in mixture, but have the objection that the chlorine atom in the compound may slowly. combine withtthe alkaline catalyst enrployed in oxyethylation. Suitablesolvents may be selected from this group for molecular weight determinations. l j

The use of such solvents is a convenient expedient in the manufacturejof the thermoplastic resins, particularly since the solvent givesarmore liquid reaction,mass and thus prevents overheating, and also because the solvent can be employed in connection witha reflux condenser and a water trap to assist in the removal of water 'of reaction and also water-present as part of the formaldehyde reactantwhenan aqueous solution of formaldehyde is used. Such aqueous solution, of course, with the ordinary product of commerce containing about 37 /2% to 40% formaldehyde, is the preferredreactant. When such solvent is used it is advantageously added at the beginning of the resinifi'c'ation procedure, or before the reaction has proceeded very far.

The solvent can be removed afterwards by distillation with or without the use of vacuum, and a final higher temperature can be employed to complete reaction, if-desired. In many instances it is most desirablejgto permit part of the solvent, particularly when it is inexpensive, e. g., xylene, to remain behind in a predetermined amount so as to have a resin which can be handled more conveniently in the oxyalkylation stage. If a more expensive solvent, such as decalin, is employed, xylene or other inexpensive solvent may be added after the removal of decalin, if desired.

Reference has been made to the word fusible. Ordinarily a thermoplastic resin is identified as one which can be heated repeatedly and still not lose its thermoplasticity. It is recognized, however, that one may-have a resin which is initially thermoplastic, but on repeated heating, may become insoluble in an organic solvent, or at least no longer thermoplastic, due to the fact that certain changestake place very slowly. As far as the present invention is concerned, it is obvious that a resin, to be suitable, needs only be sufiiciently fusible to permit processing to produce our oxyalkylated products and not yield insolubles or cause insolubilization or gel formation, or Thus,

11 not'necessarily thermoplastic in'the-most rigid sense that such-terminology would be applied to the mechanical properties or a-resin. are useful intermediates. The bulk-of all fusible resins of the kind herein described are-thermoplastic.-

The fusible or thermoplastic resins, or solvent-soluble resins, herein employed as reactants, are water-insoluble, or have no appreciable hydrophile properties. The hydrophile property is introduced by oxyalkylation. In the hereto appended claims and elsewhere the expression water-insoluble) is used to point out this characteristic of the resins. used.

Previous reference has been made to organic solvent-soluble resins, such as Novolalzs and resoles of the kind obtained exclusively from difunctional phenols. The present invention involves at least three types of resins which have been specified in detail. All these may be considered as members of the broad generic class of organic solvent-soluble, fusible phenol-aldehyde resins contemplated in our two aforementioned co-pending applications Serial Nos. 8,722 and 8,723. Inall such instances, the resin consists-of .discrete or separate molecules, as .difierentiated from .a completelycross-linked resin. Frusibility and solubility in an organic solventare characte'risticofthis state of subdivision.

Example 1 Grams Cardanol (vacuum distilledLl 576 Paracresol "-154 Phenol- 4'1 Formaldehyde (37%) 240 Concentrated HCl 4;5

Monoalkyl (Cw-C20, principally "Cm-C14) benzene monosulfonic acid sodiumsalL- 3 (Examples of alkylaryl sulfonic acids which serve as catalysts and as emulsifiers. particularly in the form of sodium. salts. include the following:

(R is an akyl hydrocarbon radical having 12-14 carbon atoms.

(R is an alkyl radical having 3-12 carbon atoms and n represents the numeral 3, 2, or 1, usually .2, in such instances where R contains less than .8 carbon atoms.

(With respect to alkylaryl sulfonicacids or the sodium salts, we have employed a monoalkylated benzene mon sulfonic acid or the sodium salt thereof, wherein the alkyl group contains to 14 carbon atoms. We have found equally effective and interchangeable the following specific sulfonic acids or their sodium salts: A mixture of diand tripropylated naphthalene monosulfonic acid; diamylated naphthalene monosulfonic acid; and ncnyl naphthalene monosulfonic acid.)

The equipment used was a conventional twopiece laboratory resin pot. The cover part of the equipment had four openings: one for refiux condenser; one for the stirring'device; one for a separatory funnel or other means of adding reactants; and a thermometer well. In the manipulation employed, the separatory funnel insert for adding reactants "was not used. The

device was equipped with-a combination reflux and water-trap apparatus so that the single piece of apparatus could be used as either a reflux condenser or a water trap, depending upon the position of the three-way glass stop-cock. This permitted convenient withdrawal of water from the water trap. The equipment, furthermore, permitted any setting of the valve without disconnecting the equipment. The resin pot was heated with a glass fibre electrical heater constructed to fit snugly around the resin pot. Such heaters, with regulators, are readily available.

The phenol-formaldehyde acid catalyst (acid and sulfonate salt in combination) and solvent were combined in the resin'potdescribed. This particular resin was a reddish-black liquid, hav ing a viscosity comparable to that of ordinary oil or slightly in excess thereof. Heat was applied, with gentle stirring, and the temperature was raised to -85 C.,'at which point a mild exo thermic reaction took place. This reaction raised the temperature to approximately -110 C. The reaction mixture was then permitted to reflux at 100-105 Qfor-approximatelythree and a half hours. The reflux trap-arrangementwas then changed from the'refiux'position to the-normal water entrapment position. The water'of solution and the water of reaction'were permitted to distil out and-collectin the trap. As the water distilled out, the temperature "gradually increased to approximately 1501C. which required-between 1.5 to 2 'hours,: At this point the water recovered in the trapyaftermaking allowance"for-a small amount-of waterheldup 'in the solvent-corresponded to thecxpected-quantity.

The solvent solution so obtainedwasused' as such in subsequent oxyalkylation steps. We have also'removed the solvent by conventional means, such as evaporation, distillation or vacuum distillation. and we customarily take a small sample of the solvent solution and evaporate the solvent tonote the characteristics of the solvent-free resin. The xylene-free resin obtained wasreddish-black in color, and soft to pliable in consistency.

Example 2 Grams Cardanol (vacuum distilled) 144 Para-nonylphenol V 264 Metacresol 32.4 Formaldehyde (37%) 162 Ammonia (26 Baum or about 28%) 21 Xylene 350 All these items were mixed together and refluxed for 6 hours, followed by removal of water by distillation and heating to C. for approximately 4 hours, forming a pliable or semi-solid resin. The reactants were, of course, stirred during the reflux period. The resin so obtained was thermoplastic and soluble in xylene.

Example 3' Grams Cardanol (vacuum distilled) 288 Ortho or paracresol 27 Metacresol 2'7 Concentrated sulfuric acid 3 Acetaldehyde 66 Xylene 100 The phenol, acid catalyst, and 50 grams of xylene were combined in the resin pot previously described under Example 1*. The initial mixture did not include the aldehyde. The mixture was heated, with stirring, to approximately C. and permitted to reflux.

' phenol,

-'ortho or para-cresol.

' Theremainder of the xylene- 50' gramsikes thenmixed with the acetaldehyde, and'this mixtures'was added slowly to the materials in the resin pot, with constant stirringjby means of the separatory funnel arrangement previously mentioned in the description of the resin pot in Example 1 Approximately 30 minutes wererequired to add this amount of diluted aldehyde A mild exothermic reaction was noted at the first addition of the aldehyde. The temperature slowly dropped, as water of reaction formed, to about 100 to 1 10 C., with the reflux temperature being determined by the boiling point of water. After all the aldehyde had been added, the reactants were permitted to reflux for between an hour to an hour and a half before removing the water by means of the trap arrangement. After the water was removed, the remainder of the procedure was essentially the same as in Example 1 v The solvent-free re in was reddish-black in color and comparatively soft. V

In similar procedures where the amount of xylene is different, for instance, a little less or a little more,.as the'occasion may require, we have stillemployed 50 grams of xylene-in the' initial step and all the residual xylene is then added in ,the second stage.

Example 4 JThesame procedure was followed as in Example 3 except that the amount of cardanol employed was reducedto 268.2 grams, and the amount of cresol increased to 178.8 grams, of

which one-third was metacresol and two-thirds ortho 'or para-cresol, or a mixture thereof,

Example 5 Example '6 The same procedure was followed as in Examples 3 4 and 5, except that para-ethylpara-propylphenol, para-butylphenol, para-amylphenol, or para-octylphenol was substituted in molarequivalent amounts for the Example 7 U V V Grams Cardanol 288 Para-ethylphenol 35.5 Phenol 23.5 Acetaldehyde 66 Concentrated sulfuric acid 3 Xylene 100 The procedure followed was the same as that described in Example 3 p The procedure followed was the same as described in Example 3*. The final product was a soft, amber-colored resin. The same procedure '14 as in the two preceding examples, but with the use-of normal butyraldehyde and normal heptal dehyde'in molar quantitiesto replace the acetaldehyde, gives resulting resins of the same general appearance.

The procedure followed was the same as that in Example 1 Example 10 -The same procedure was followed as in the preceding example, except that the para-ethylphenol was replaced by the equivalent molar amount of para-propylphenol, para-butylphenol, para octylphenol, para amylphenol, paraphenylphenol, or other difunctional phenol. Further variants include' the replacement of the phenol by a molar equivalent amount of metac-resol or other low alkyl phenol, for instance, ethyl or propylphenol, provided the alkyl group is in' the meta position.

e i I I Example 11 The same procedure was followed as in Examples 9 and 10 except that the molal ratio of cardanol to the other phenols (difunctional and trifunctional phenols) was changed from 3 to 2, to 2 to 2 with the same molar proportion of total phenols. Otherwise, the same reactants and same procedures were employed,

Example 1.2

The same procedure was followed as in EX- amples 9 and 10 except that the molal ratio of cardanol to the other phenols (difunctional and trifunctional phenols) was changed from 3 to 2, to 2 to 3, with the same molar proportion of total The procedure followed was the same as in Example 1 The resulting resin was semi-solid, tacky, and of heavy tar-like consistency.

Example 14 Examples 1 and2 preceding, were repeated, replacing cardanol by hydrogenated cardanol. Since the commercial product was not 100% pure, .it wasnot necessary to make any change 1 in proportions because of the slight difference in molecular. weightv between hydrogenated cardanol and cardanol. However, allowance for this slightincrease .can be. made. a

EzzzamplelS Grams Chlorinated cardanol 1'71 Menthylphenol 116 Metacresol 19 Butyraldehyde 84.5 Concentrated sulfuric acid 3 Xylene 250 resin pot by the same procedure used as in Example 3 The solvent-free resin was soft and dark red in appearance. See what is said under Example 3 preceding.

Example 16 v Grams Cardanol (vacuum distilled) 195 j Nonylphenol 330 Metacresol 8.1 Formaldehyde (37%) r 203- Catalyst None Xylene 450 The above ingredients were placed in an autoclave with a stirrer and heated to approximately 160 C., and stirred for'4 hours. The pressure during this time varied from 105 to 125 pounds per square inch gauge pressure. The resultant product was a thick reddish material, having somewhat gummy or rubbery characteristics. To this were added 1000 grams of xylene and heated for an hour at 160 C. under pressure of 100 pounds per square inch so as to give a complete solution. This solution was then treated in the following manner: The solution was diluted further by the addition of 2100 grams of xylene. This dilute xylene solution was divided into three parts, and each third handled separately. The procedure was simply to wash approximately three times with an equal volume of water and then remove the xylene under mm. (Hg) pressure until the xylene was 55%. The solvent-free resin was reddish-black in color and soft to semi-pliable in consistency.

The procedure employed was the same as described under the heading of Example 15 preceding. The resin was reddish-black in color and semi-fluid to pliable in consistency.

Example 18 Grams Cardanol (vacuum distilled) 144 Para-octylphenol 103 Metacresol 19 -Butyra1dehyde 84.5 Concentrated sulfuric acid 4.0 Xylene 225 516 The procedure employed was that described under the heading Example 15, preceding. .The resin was reddish-black in color and semi-soft to pliable in consistency.

i Example 19 1 Cardanol (vacuum distilled) 144- Metacresol 19 Nonylphenol n Butyraldehyde- 84.5 Concentrated sulfuric acid 4.0 Xylene 250 The procedure followed was the same as "described under the heading of Example 15 ..preceding. The solvent-free resin was soft to semi tacky in appearance and reddish-black in color. .The solution, as prepared, contained 42.5% xylene.

Example 20 Grams Cardanol. (vacuum distilled) 245 Nonylphenol 187 Metacresol 32.4 Furfural V. 192 Fotassiumcarbonate 1 .12

The furfural was shaken with dry sodium carbonate prior to use, to eliminate any acids, etc. The procedure employed was substantially that described in detail in Technical Bulletin No. 109 of the Quaker Oats Co., Chicago, Ill. The above .reactants. were heated under the reflux condenser for 2 hours in the same resin pot arrangement described in Example 1 :The separatory funnel device was not employed-No xylene or other solvent was added at this stage. The amount of material vaporized and condensed was comparatively small, except for thewater of reaction. At the end of this heating or. reflux period, the trap was set to remove the .water. The maximum temperature during and after re.- moval of water was approximately 202 C. The material in the trap represented 32 cc. water and 2.5 cc. furfural. At this point 250 grains of xylene were added'so as'to' give a suitable solution. The resin was reddish-black in color, xylene-soluble and semi-soft or tacky in consistency. The solution, as prepared, contained approximately 28% xylene.

Example 21 e Grams Cardanol (vacuum distilled) 245 Menthylphenol 197 Metacresol 32.4 Heptaldehyde 228 Concentrated sulfuric acid 8 Xylene 350 The procedure followed was the same as described under the heading of Example 15 preceding. The resin was reddish-amber in color and very viscous or almost suggestive of a solid.

Example 22 The procedure followed was that described under Example 3, preceding. The resin was dark to reddish-black in appearance, semi-solid in consistency, and the solution, as prepared, contained 20% xylene.

Example 24 Grams Cardanol (vacuum distilled) 144 Nonylphenol 220 Metacresol 28.5 Benzaldehyde 187 Concentrated sulfuric acid 4.5 Xylene 350 The procedure employed was that described under the heading of Example 15 preceding. The solvent-free resin was reddish-black in color and semi-soft to pliable in consistency. The resin, as prepared, contained 38.9% xylene.

As far as the manufacture of resins is concerned, it is usually most convenient to employ a catalyst such as illustrated by previous examples. Previous reference has been made to the use of a single phenol of each type or a single aldehyde, or a single oxyalkylating agent.

Obviously, mixtures of reactants may be employed, as has been illustrated, at least in part, in some previous examples. If desired, a mixture of cardanol and hydrogenated cardanol could be employed. Likewise, a mixture of phenol and metacresol or a mixture of amylphenol and butylphenol.

It is extremely difiicult to depict the structure of a resin made from a single difunctional phenol, as, for example, from para-amylphenol and formaldehyde. When a mixture of phenols is used, and this is particularly true when such mixtures are selected exclusively from trifunctional phenols having a long chain substituent in the meta position, or at least, include a considerable amount of such phenol, one runs into even greater complexity of structure.

If a mixture of aldehydes is employed, for instance, acetaldehyde and butyraldehyde, or acetaldehyde and formaldehyde, or benzaldehyde and acetaldehyde, the final structure of the resin becomes even more complicated and possibly depends upon the relative reactivity of the aldehyde. For that matter, one might be producing simultaneously two different resins in what would actually be a mechanical mixture, although such mixture might exhibit some unique properties, as compared with a mixture of the same two resins prepared separately. Similarly, as has been suggested, one might use a combination of oxyalkylating agents; for instance, one might partially oxyalkylate with ethylene oxide and then finish off with propylene oxide. It is understood that the use of oxyalkylated derivatives of such resins, derived from such plurality of reactants, instead of being limited to a single reactant from each of the three classes, is contemplated and here included, for the reason that they are obvious variants.

Having obtained a suitable resin of the kind described, such resin is subjected to treatment l8 with a low molal reactive alpha-beta olefine oxide, so as to render the product distinctly hydrophile in nature, as indicated by the fact that it becomes self-emulsifiable or miscible or soluble in water, or self-dispersible, or has emulsifying properties; The olefine oxides employed are characterized by the fact that they contain not over 4 carbon atoms and are selected from the class consisting of ethylene oxide, propylene oxide, butylene oxide, glycide, and methyl-glycide. Glycide may be, of course, considered as a hydroxypropylene oxide and methyl glycide as a hydroxy butylene oxide. In any event, however, all such reactants contain the reactive ethylene oxide ring and may be best considered as derivatives of or substituted ethylene oxides. The solubilizing efiect of the oxide is directly proportional to the percentage of oxygen present, orspecifieally, to the oxygen-carbon ratio.

In ethylene oxide, the oxygen-carbon ratio is 1:2. In glycide, it is 2:3; and in methyl glycide, 1:2. In such compounds, the ratio is very favorable to the production of hydrophile or surfaceactive properties. However, the ratio, in propylene oxide, is 1:3, and in butylene oxide, 1:4. I Ob viously, such latter two reactants are satisfactorily employed only where the resin composition is such as to make incorporation of the desired property practical. In other cases, they may produce marginally satisfactory derivatives, or even unsatisfactory derivatives. They are usable in conjunction with the three more favorable alkylene oxides in all cases. For instance, after one or several propylene oxide or butylene oxide molecules have been attached to the resin molecule, oxyalkylation may be satisfactorily continued using the more favorable members of the class, to produce the desired hydrophile product. Used alone, these two reagents may in some cases fail to produce sufficiently hydrophile derivatives because of their relatively low oxygen-carbon ratios.

Thus, ethylene oxide is much more effective than propylene oxide, and propylene oxide is more effective than butylene oxide. I-Iydroxy propylene oxide (glycide) is more efiective than propylene oxide. Similarly, hydroxy butylene oxide (methyl glycide) is more effective than butylene oxide. Since ethylene oxide is the cheapest alkylene oxide available and is reactive, its use is definitely advantageous, and especially in light of its high oxygen content. Propylene oxide is less reactive than ethylene oxide, and butylene oxide is definitely less reactive than propylene oxide. On the other hand, glycide may react with almost explosive violence and must be handled with extreme care.

The oxyalkylation of resins of the kind from which the products used in the practice of the present invention are prepared is advantageously catalyzed by the presence of an alkali. Useful alkaline catalysts include soaps, sodium acetate, sodium hydroxide, sodium methylate, caustic potash, etc. The amount of alkaline catalyst usually is between 0.2% to 2%. The temperature employed may vary from room temperature to as high as 200 C. The reaction may be .601 ducted with or without pressure, i. e., from zero pressure to approximately 200 or even 300 pounds gauge pressure (pounds per square inch). In a general way, the method employed is substantially the same procedure as used for oxyalkylation of other organic materials having reactive phenolic groups.

It may be necessary to allow for the acidity 19 1 of a resin in determining the amount of alkaline catalyst to be added in oxyalkylation. For instance, if a nonvolatile strong acid such as sulfuric acid is used to catalyze the resinification reaction, presumably after being converted into a sulfonic acid, it may be necessary and is usually advantageous to add an amount of alkali equal stoichiometrically to such acidity, and include added alkali over and above this amount as the alkaline catalyst.

It is advantageous to conduct the oxyethylation in presence of an inert solvent such as xylene, cymene, decalin, ethylene glycol diethylether, diethyleneglycol diethylether, or the like, although with many resins, the oxyalkylation proceeds. satisfactorily without a solvent. Since xylene is cheap and may be permitted to be present in the final product used as a demulsifier, it is our preference to use xylene. This is particularly true in the manufacture of products from low-stage resins, i. e., of 3 and up to and including 7 units per molecule.

' If a xylene solution is used in an autoclave as hereinafter indicated, the pressure readings of course represent total pressure, that is, the combined pressure due to xylene and also due to ethylene oxide or whatever other oxyalkylating agent is used. Under such circumstances it may be necessary at times to use substantial pressures to obtain efiective results, for instance, pressures up to 300 pounds along with correspondingly high temperatures, if required.

However, even in the instance of high-melting resins, a solvent such as xylene can be eliminated in either one of two ways: After the introduction of approximately 2 or 3 moles of ethylene oxide, for example, per phenolic nucleus, there is a def nite drop in the hardness and melting point of the resin. At this stage, if xylene or a similar solvent has been added, it can be eliminated by distillation (vacuum distillation if desired) and the subsequent intermediate, being comparatively soft and solventfree, can be reacted further in the usual manner with ethylene oxide or some other suitable reactant.

Another procedure is to continue the reaction to completion with such solvent present and then eliminate the solvent by distillation in the customary manner.

Another suitable procedure is to use propylene oxide or butylene oxide as a solvent as well as a reactant in the earlier stages along with ethylene oxide, for instance, by dissolving the powdered resin in propylene oxide even though oxyalkylation is taking place to a greater or lesser degree. After a solution has been obtained which represents the original resin dissolved in propylene oxide or butylene oxide, or a mixture which includes the oxyalkylated product, ethylene oxide is added to react with the liquid mass until hydrophile properties are obtained. Since ethylene oxide is more reactive than propylene oxide or butylene oxide, the final product may contain some unreacted propylene oxide or butylene oxide which can be eliminated by volatilization or distillation in any suitable manner.

Attention is directed to the fact that the resins herein described must be fusible or soluble in an organic solvent. Fusible resins invariably are soluble in one or more organic solvents such as those mentioned elsewhere herein. It is to be emphasized, however, that the organic solvent employed to indicate or assure that the resin meets this requirement need not be the one used in oxyalkylation. Indeed solvents which are susceptible to oxyalkylation are included in this group of organic solvents. Examples of such solvents are alcohols and alcohol-ethers. However, where a resin is soluble in an organic solvent, there are usually available other organic solvents which are not susceptible to oxyalkylation, useful for the oxyalkylation step. In any event, the organic solvent-soluble resin can be finely powdered, for instance to 100 to 200 mesh, and a slurry or suspension prepared in xylene or the like, and sub ected to oxyalkylation. The fact that the resin is soluble in an organic solvent or the fact that it is fusible means that it consists of separate molecules. Phenol-aldehyde resins of the type herein specified possess reactive hydroxyl groups and are oxyalkylation susceptible.

Considerable of what is said immediately hereinafter is concerned with the ability to vary the hydrophile properties of the compounds used in the process from minimum hydrophile properties to maximum hydrophile properties. Even more remarkable, and equadv difiicult to explain, are the versatility and utility of these compounds as one goes from minimum hydrophile property to ultimate maximum hydrophile property. For instance, minimum hydrophile property may be described roughly as the point where two ethyleneoxy radicals or moderately in excess thereof are introduced per phenolic hydroxyl. Such minimum hydrophile property or sub-surfaceactivity or minimum surface-activity means that the product shows at least emulsifying properties or self-dispersion in cold or even in warm distilled water (15 to 40 C.) in concentrations of 0.5% to 5.0%. These materials are generally more soluble in cold water than warm water, and may even be very insoluble in boiling water. Moderately high temperatures aid in reducing the viscosity of the solute under examination. Sometimes ifone continues to shake a hot solution, even though cloudy or containing an insoluble phase, one finds thatsolution takes place to give a homogeneous phase as the mixture cools. Such self-dispersion tests are conducted in the absence of an insoluble solvent.

When the hydrophile-hydrophobe balance is above the indicated minimum (2 moles of ethylene oxide per phenolic nucleus or the equivalent) but insuiiicient to give a sol as described immediately receding, then, and in that event hydrophile properties are indicated by the fact that one can produce an emulsion by having present 10% to 50% of an inert solvent such as xylene. All that one need to do is to have a xylene solution within the range of 50 to parts by weight of oxyalkylated derivatives and 50 to 10 parts by weight of xylene and mix such solution with one, two or three times its volume of distilled water and shake vigorously so as to obtain an emulsion which may be of the oil-in-water type or the water-in-oil type (usually the former) but, in any event, is due to the hydrophile-hydrophobe balance of the oxyalkylated derivative. We prefer simply to use the xylene diluted derivatives, which are described elsewhere, for this test rather than evaporate the solvent and employ any more elaborate tests, if the solubility is not sufficient to permit the simple sol test in water previously noted.

If the product is not readily watersoluble it may be dissolved in ethyl or methyl alcohol, ethylene glycol diethylether, or diethylene' glycol diethylether,.with alittle acetone added if required,

making a rather concentrated solution, for instance 40% to 50%, and then adding enough of the concentrated alcoholic or equivalent solution to give the previously suggested 0.5% to 5.0% strength solution. If the product is self-dispersing (1. e., if the oxyalkylated product is a liquid or a liquid solution self-emulsifiable), such sol or dispersion is referred to as at least semistable in the sense that sols, emulsions, or dispersions prepared are relatively stable, if they remain at least for some period of time, for instance 30 minutes to two hours, before showing any marked separation. Such tests are conducted at room temperature (22 C.). Needless to say, a test can be made in presence of an insoluble solvent such as to of xylene, as noted in previous examples. If such mixture, i. e., containing a water-insoluble solvent, is at least semistable, obviously the solvent-free product would be even more so. Surface-activity representing an advanced hydrophile-hydrophobe balance can also be determined by the use of conventional measurements hereinafter described. One outstanding characteristic property indicating surface-activity in a material is the ability to form a permanent foam in dilute aqueous solution, for example, less than 0.5%, when in the higher oxyalkylated stage, and to form an emulsion in the lower and intermediate stages of oxyalkylation.

Allowance must be made for the presence of a solvent in the final product in relation to the hydrophile properties of the final product. The principle involved in the manufacture of the herein contemplated compounds for use as demulsifying agents, is based on the conversion of a hydrophobe or non-hydrophile compound or mixture of compounds into products which are distinctly hydrophile, at least to the extent that they have emulsifying properties or are self-emulsifying; that is, when shaken with water they prgduce stable or semi-stable suspensions, or, in the presence of a water-insoluble solvent, such as xylene,

an emulsion. In demulsification, it is sometimes preferable to use a product having markedly enhanced hydrophile properties over and above the initial stage of self-emulsifiability, although we have found that with products of the type used herein, most efficacious results are obtained with products which do not have hydrophile properties beyond the stage of self-dispersibility.

More highly oxyalkylated resins give colloidal solutions or sols which show typical properties comparable to ordinary surface-active agents. Such conventional surface-activity may be measured by determining the surface tension and the interfacial tension against paraffin oil or the like. At the initial and lower stages of oxyalkylation, surface-activity is not suitably determined in this same manner, but one may employ an emulsification test. Emulsions come into existence, as a rule, through the presence of a surface-active emulsifying agent. Some surface-active emulsifying agents such as mahogany soap may produce a water-in-oil emulsion or an oil-in-water emulsion, depending upon the ratio of the two phases, degree of agitation, concentration of emulsifying agent, etc.

The same is true in regard to the oxyalkylated resins herein specified, particularly in the lower stage of oxyalkylation, the so-called sub-surfaceactive stage. The surface-active properties are readily demonstrated by producing a xylene-water emulsion. A suitable procedure is as follows: The oxyalkylated resin is dissolved in an equal weight of xylene. Such -50 solution is then mixed with 1-3 volumes of water and shaken to produce an emulsion. The amount of xylene is invariably sufiicient to reduce even a tacky resinous product to a solution which is readily dispersible. The emulsions so produced are usually xylene-in-water emulsions (oil-in-water .type) particularly when the amount of distilled water used is at least slightly in excess of the volume of xylene solution and also if shaken vigorously. At times, particularly in the lowest stage of oxyalkylation, one may obtain a water-in-xylene emulsion (water-in-oil type) which is apt to reverse on more vigorous shaking and further dilution with water.

If in doubt as to this property, comparison with a resin obtained from para-tertiary butylphenol and formaldehyde (ratio 1 part phenol to 1.1

formaldehyde), using an acid catalyst and then followed by oxyalkylation, using 2 moles of ethylene oxide for each phenolic hydroxyl, is helpful. The procedure followed in preparing such a standard resin for comparison was the same procedure as described in Example 1 preceding. A specific example of ingredients suitable for making such resin is as follows:

Monoalkyl (Clo-C20, principally C12-C14) benzene monosulfonic acid sodium salt Xylene Such resin, prior to oxyalkylation, has a molecular weight indicatingabout 4 units per resin molecule. Such resin, when diluted with an equal weight of xylene, will serve to illustrate the above emulsification test.

In a few instances, the resin may not be suificiently soluble in xylene alone, but may require the addition of some ethyleneglycol diethylether, as described elsewhere. It is understood that such mixture, or any other similar mixture, is considered the equivalent of xylene for the purpose of this test.

In 'many cases there is no doubt as to the presence or absence of hydrophile or surfaceactive characteristics in the products used in accordance with this invention. They dissolve or disperse in water; and such dispersions foam readily. With borderline cases, i. e., those which. show only incipient hydrophile or surface-active propert (sub-surface-activity) tests for emul sifying properties or self-dispersibility are useful. The fact that a. reagent is capable of producing a dispersion in Water is proof that it-- is distinctly hydrophile. In doubtful cases, com parison can be made with the butylphenolformaldehyde resin analog wherein 2 moles of ethylene oxide have been introduced for each phenolic nucleus.

The presence of xylene or an equivalent waterinsoluble solvent may mask the point at which a solvent-free product on mere dilution in a, test tube exhibits self-emulsification. For this reason, if it is desirable to determine the approximate point where self-emulsification begins, then it is better to eliminate the xylene or equivalent from a small portion of the reaction mixture and test such portion. In some cases, such xylene-free resultant may show initial or incipient hydrophile properties, Whereas in presence of xylene such properties would not be noted. In other cases, the first objective indication of hydrophile properties may be the capacity of the material to emulsify an insoluble solvent such as xylene. It is to be emphasized that hydrophile properties herein referred to are such as those exhibited by incipient self-emulsification or the presence of emulsifying properties and go through the range of homogeneous dispersibility or admixture with water even in presence of added water-insoluble solvent and minor proportions of common electrolytes as occur in oil field brines.

Elsewhere, it is pointed out that an emulsification test may be used to determine ranges of surface-activity and that such emulsification tests employ a xylene solution. Stated another way, it is reall immaterial whether a Hlene solution produces a sol orwhether it merely produces an emulsion.

In light of what has been said previously in regard to the variation of range of hydrophile properties, and also in light of what has been said as to the variation in the effectiveness of various alkylene oxides, and most particularly of all ethylene oxide, to introduce hydrophile character, it becomes obvious that there is a wide variation in the amount of alkylene oxide employed, as long as it is at least 2 moles per phenolic nucleus, for producing products useful for the practice of this invention. Another variation is the molecular size of the resin chain resulting from reaction between the difunctional phenol and the aldehyde such as formaldehyde. It is well known that the size and nature or structure of the resin polymer obtained varies somewhat with the conditions of reaction, the proportions of reactants, the nature of the catalyst, etc.

Based on molecular weight determinations, most of the resins prepared as herein described, particularly in the absence of a secondary heating step, contain 3 to 6 or '7 phenolic nuclei with approximately 4 or 5 nuclei as an average. More drastic conditions of resinification yield resins of greater chain length. Such more intensive resinification is a conventional procedure and may be employed if desired. Molecular\ weight, of course, is measured by any suitable procedure, particularly by cryoscopic methods; but using the same reactants and using more drastic conditions of resinification one usually finds that higher molecular weights are indicated by higher melting points of the resins and a tendency to decreased solubility. been said elsewhere herein in regard to a secondary step involving the heating of a resin with or without the use of vacuum.

, We have previously pointed out that either an alkaline or acid catalyst is advantageously used in preparing the resin. A combination of catalysts is sometimes used in two stages; for instance, an alkaline catalyst is sometimes employed in a first stage, followed by neutralization and addition of a small amount of acid catalyst in a second stage. It is generally believed that even in the presence of an alkaline catalyst, the number of moles of aldehyde, such as formaldehyde, must be greater than the moles of phenol employed in order to introduce methylol groups in the intermediate stage. There is no indication that such groups appear in the final resin if prepared by the use of an acid catalyst. It is possible that such groups may appear in the finished resins prepared solely with an al kaline catalyst; but we have never been able to confirm this fact in an examination of a large number of resins prepared by ourselves. Our preference, however, is to use an acid-catalyzed resin, par- See what has L ticularly employing a, formaldehyde-to-phenol ratio of 0.95 to 1.20 and, as far as we have been able to determine, such resins are free from methylol groups. As a matter of fact, it is probable that in acid-catalyzed resinifications, the methylol structure may appear only momentarily at the very beginning of the reaction and in all probability is converted at once into a more complex structure during the intermediate stage.

One procedure which can be employed in the use of a new resin to prepare products for use in the process of the invention is to determine the hydroxyl value by the Verley-Biilsing method or its equivalent. The resin, as such, or in the form of a solution, as described, is then treated with ethylene oxide in the presence of 0.5% to 2% of sodium methylate, as a catalyst, in stepwise fashion. The conditions of reaction, as far as time or percent is concerned, are within the range previously indicated. With suitable agitation the ethylene oxide, if added in molecular proportion, combines within a comparatively short time, for instance, a few minutes to 2 to 6 hours, but in some instances, requires as much as 8 to 24 hours. A useful temperature range is from 125 to 225 C. The completion of the reaction of each addition of ethylene oxide in stepwise fashion'is usually indicated by the reduction or elimination of pressure. An amount conveniently used for each addition, is generally equivalent to a mole or two moles of ethylene oxide per hydroxyl radical. When the amount of ethylene oxide added is equivalent to approximately by weight, of the original resin, 2. sample is tested for incipient hydrophile properties, by simply shaking up in water as is, or after the elimination of the solvent, if a solvent is present. The amount of ethylene oxide used to obtain a useful demulsifying agent, as a rule, varies from by weight, of the original resin, to as much as five or six times the weight of the original resin. In the case of a resin derived from para-tertiary butylphenol from cardanol, hydrogenated cardanol, etc., in combination with a difunctional phenol, as well as a trifunctional phenol, as herein described, as little as 50%, by weight, of ethylene oxide may give suitable solubility. With propylene oxide, even a greater molecular proportion is required and sometimes a resultant of only limited hydrophile properties is obtainable. The same is true to even a greater extent with butylene oxide. The hydroxylated alkylene oxides are more effective in solubilizing properties than the comparable compounds in which no hydroxyl is present.

Attention is directed to the fact that in the subsequent examples reference is made to the stepwise addition of the alkylene oxide, such as ethylene oxide. It is understood, of course, there is no objection to the continuous addition of alkylene oxide until the desired stage of reaction is reached. In fact, there may be less of a hazard involved and it is often advantageous to add the alkylene oxide slowly in a continuous stream and in such amount as to avoid exceeding the higher pressures noted in the various examples or elsewhere.

It may be well to emphasize the fact that when resins are produced from difunctional phenols and some of the higher aliphatic aldehydcs, such soft orpitch-like resin at ordinary temperatures.

Such resins become comparatively fluid at to C. as a rule, and thus can be readily oxy- I described.

alkylated preferably oxyethylated, without the use of a solvent.

What has been said previously is not intended to suggest that any experimentation is necessary to determine the degree of oxyalkylation, and particularly oxyethylation. What has been said previously is submitted primarily to emphasize the fact that these remarkable oxyalkylated resins having surface activity show unusual properties as the hydrophile character varies from a minimum to an ultimate maximum. One should not underestimate the utility of any of these products in a surface-active or sub-surface-active range without testing them for demulsification. A few simple laboratory tests which can be conducted in a routine manner will usually give all the information that is required.

For instance, a simple rule to follow is to prepare a resin having at least three phenolic nuclei and being organic solvent-soluble. Oxyethylate such resin, using the following four ratios of moles of ethylene oxide per phenolic unit equivalent: 2 to 1; 6 to 1; 10 to 1; and 15 to 1. From a sample of each product remove any solvent that may be present, such as xylene. Prepare 0.5% and 5.0% solutions in distilled water, as previously indicated. A mere examination of such series will generally reveal an approximate range of .minimum hydrophile character, moderate hydrophile character, and maximum hydrophile character. If the 2 to 1 ratio does not show minimum hydrophile character by test of the-solventfree product, then one should test its capacity to form an emulsion when admixedwith xylene or other insoluble solvent. If neither test shows the required minimum hydrophile property, repetition using 2 to 4 moles per phenolic nucleus will serve. Moderate hydrophile character should be shown by either the 6 to 1 or 10 to 1 ratio. Such moderate hydrophile character is indicated by the fact that the sol in distilled water within the previously mentioned concentration range is a permanent translucent sol, when viewed in a comparatively thin layer, for instance, the depth of a test tube. Ultimate hydrophile character is usually shown at the 15 to 1 ratio test, in that adding a small amount of an insoluble solvent, for instance, of xylene, yields a product which will give, at least temporarily, a transparent or tran lucent sol of the kind just described. The formation of a permanent foam, when a 0.5% to 5.0% aqueous solution is shaken, is an excellent test for surface activity. Previous refer: ence has been made to the fact that otheroxy alkylating agents may require the use of increased amounts of alkylene oxide. However, if one does not even care to go to the trouble of calculating molecular weights, one can simply arbitrarily prepare compounds containing ethylene oxide equivalent to about 50% to 7 by weight, for example, 65%, by weight, of the resin to be oxyethylated; a second example using approximately 200 to 300% by weight, and a third example, using about 500% to 750%, by weight, to explore the range of hydrophile-hydrophobe balance.

A practical examination of the factor of oxyalkylation level can be made by a. very simple test, using a pilot plant autoclave having a capacity of about 10 to gallons, as hereinafter Such laboratory-prepared routine compounds can then be tested for solubility, and generally speaking, this is all that is required to give a suitable variety covering the hydrophilehydrophobe range. All these tests, as stated, are

intended to be routine tests and nothing more. They are intended to teach a person, even though unskilled in oxyethylation or oxyalkylation, how to prepare, in a perfectly arbitrary manner, a series of compounds illustrating the hydrophilehydrophobe range.

Ordinarily, the oxyalklation is carried out in autoclaves provided with agitators or stirring devices. We have found that the speed of the agitation markedly influences the time of reaction. In some cases, the change from slow speed agitation, for example, in a laboratory autoclave agitation with a stirrer operating at a speed of 60 to 200 R. P. M. to high speed agitation, with the stirrer operating at 250 to 350 R. P. M. reduces the time required for oxyalkylation by about one-half to two-thirds. Frequently xylene-soluble products which give insoluble products by procedures employing comparatively slow speed agitation give suitable hydrophile products, when produced by similar procedure, but with high speed agitation, as a result, we believe of the reduction in the time required, with consequent elimination or curtailment of opportunity for curing or etherization. Even if the formation of an insoluble product is not involved, it is frequently advantageous to speed up the reaction, thereby reducing production time, by increasing agitating speed. In large scale operations we have demonstrated that economical manufactur- 'ing results from continuous oxyalkylation, i. e.,

an operation in which the alkylene oxide is continuously fed to the reaction vessel, with high speed agitation, i. e., an agitator operating at 250 to 350 R. P. M. Continuous oxyalkylation,

other conditions being the same, is more rapid than batch oxyalkylation, but the latter is ordi narily more convenient for laboratory operation.

As far as we know, some thermoplastic or fusible cardanol or mixed cardanol resins are offered in the open market for purposes other than those herein described. If one obtains such a resin, one might have to make certain determinations, in order to make the quickest approach to the appropriate oxyallwlation range. For instance, one should know (a) the molecular size, indicating the number of phenolic units; (22) the nature of the aldehydic residue, which is usually CH2; and (c) the nature of the substituent, which may be a cardanol type resin alone, or a hydrogen- -ated cardanol type, or a chlorinated cardanol H r n R R R (n=1 to 13, or even more) is given approximately by the formula: (mol. wt. of phenol 2) plus mol. wt. of methylene or substituted methylene radical. The molecular weight of the resin would be 11. times the value for the internal limit, plus the values for the terminal units. The left-hand terminal unit of the above structural formula, it will be seen, is identical with the recurring internal unit, except that it has one extra hydrogen. The right-hand terminal unit lacks the methylene bridge element. Using one internal unit of a resin as the basic element, a resins molecular weight is given approximately by taking (11. plus 2) times the'weight of the internal element. Where the resin molecule has only 3 phenolic nuclei, as in the structure shown, this calculation will be in error by several percent; but as it grows larger, to contain 6, 9 or 12 phenolic nuclei, the formula comes to be more than satisfactory.

In the instant case, such a variety of phenols may be employed that it is somewhat difficult to calculate a molecular weight, except as a statistical average. If, on the other hand, a resin is obtained from a single phenol, such as cardanol, then the molecular weight of the internal structural units of the resin of the following oversimplified formula:

OH e1. 3

OH OH H I H R R R (n -1 to 13, or even more) is given approximately bythe formula: (mol. wt. of phenol -2) plus mol. wt. of methylene or substituted methylene radical. The molecular weight of the resin would be n times the value for the internal limit, plus the values for the terminal The left-hand terminal unit of the above structural formula, it will be seen, is identical with the recurring internal unit, except that it has one extra hydrogen. The righthand terminal unit lacks themethylene bridge element. Using one internal unit of a resin as the basic element, a resins molecular weight is given approximately by taking (11. plus 2) times the weight of the internal element. Where the resin molecule has only 3 phenolic nuclei, as in the structure shown, this calculation will be in "error by several percent; but as it grows larger, to contain 6, 9 or 12 phenolic nuclei, the formula comes to be more than satisfactory. Using such an approximate weight, one need only introduce, for example, two molal weights of ethylene oxide, or slightly more, per phenolic nucleus, to produce a product of minimal hydrophile character. Further oxyalkylation gives enhanced hydrophile character. Although we have prepared and tested a large number of oxyethylated products of. the type described herein, we have found no instance where the use of less than 2 moles of ethylene oxide per phenolic nucleus give desirable products. If the resin were obtained solely from a difunctional phenol, one is presented with the problem of attempting to depict the structure which has been a matter of considerable speculation, especially where various catalysts are employed. One can, of coursaconsider 'such possible structures in light of what has been suggested for Novolaks and resoles. Actually, knowing the three phenols employed, i. e., the anacardic acid phenol, the difunctional phenol, and the trifunctional phenol, and the ratios of the two, a suitable estimate can be made in light of what has been said preceding.

The following Examples 1 through 9 are included to exemplify the production of oxyalkylat ion products of the invention from resins, specifically, resins described in nine of thefore going Examples 1 to 18*, giving exact and complete details for the carrying out of the ,pro-

The resin employed was the ammonia catalyzed resin described under the heading of Example 2, preceding. This resin was obtained from a mixture of cardanol, nonylphenol and metacresol, using formaldehyde and ammonia as the catalyst. The resin solution employed was 512 grams. The solution contained 39% xylene as a solvent. 2% of sodium methylate was used as a catalyst. The solution or suspension of the resin in the solvent, along with the catalyst, was placed in an autoclave and approximately 750 grams of ethylene oxide were added in six portions of grams each. After each portion was added, the reaction was permitted to take place for approximately one to 4 hours. All these values for each addition are shown in the subsequent table. The temperature employed varied from to C., as shown in the table. The maximum gauge pressure varied from 160 pounds per square inch to pounds per square inch, as shown in the table. At the end of each reaction period there was no further drop in pressure indicating that all the ethylene oxide present'had reacted'and the pressure registered on'the gauge represented the vapor pressure of xylene 'at the ind cated temperature. A test as to" solubility, emulsifiability, or miscibility, was made on the resultant after each addition of ethylene oxide.

In this particular operation, after the first ad dition of the ethylene oxide the product still showed the same soluble characteristics as prior to oxyethylation. After the second addition of ethylene oxide the product was somewhat emul sifiable. After the third addition of ethylene oxide, the product tended to give a curdy suspen-- sion. After the fourth addition of ethylene oxide, the product was more soluble than before, but still showed some curds. After the fifth addition of ethylene oxide, the product was almost soluble without curds; after the sixth addition of ethylene oxide the product was completely soluble without curds. Needless to say, the final product contained xylene, which, if removed, would give a composition showing even greater solubility.

In order to obtain greater solubility a second series was run in which the amount of ethylene oxide was increased by approximately 450 grams added in three further successive additions of 150 grams each. Prior to addin the second portion of ethylene oxide (450 grams) another portion of sodium methylate (6 grams) was added and the conditions of reaction were substantially the same as in the first series. After addition of the final 450 grams of ethylene oxide the product was a clear, amber-colored fluid of a viscosity somewhat less than that of castor oil and definite y lighter in color than the batch which had been prepared, using only 900 grams of ethylene oxide.

Example 2 The same reactants and procedure were employed as in Example 1 preceding,.except that 5 propylene oxide was employed instead of ethylene Oxide, The resultant, even on the addition of the alkylene oxide in the weight proportions of the previous example, has diminished hydrophile properties, in comparison with the resultants of Example 1". This illustrates the point that propylene oxide and butylene oxide give products of lower levels of hydrophile properties than does ethylene oxide.

Example 3 Example 4* The same procedure was followed as in Example l preceding, except that instead of employing the resin in Example 1, there was substituted instead the resin of Example 3 This resin obtained from cardanol. and metacresol, in admixture with either ortho or paracresol. In the particular example employed, paracresol was used; our experience has been that it does not make. any difierence, at least in this instance. The product obtained was similar in appearance, color and viscosity to that of Example 1.

Example 5 The same reactants and procedure were used as in Example 1, except tha't'th'e resin employed was that described under the heading of Example 7 This resin was obtained from-cardanol, paraethylphenol, phenol, and acetaldehyde, using sulfuric acid as a catalyst. The oxyethylated resin in color, appearance and viscosity was like that of Example 1 Example 6 The reactants and procedure employed were the same as in Example 1 except that the particular resin employed was that described under the heading of Example 8 This resin was obtained from cardanol, para-tertiarybutylphenol, phenol and acetaldehyde, using sulfuric acid as a catalyst. The physical apearance of the finished product was like that in previous examples.

Example 7 The reactants and procedure employed were the same as in Example l except that tin tetrachloride was used as a .catalyst instead of sodium methylate (see table). The particular resin employed was the one described under the heading of Example This resin was obtained from chlorinated cardanol, menthylphenol, metacresol and butyraldehyde, using sulfuric acid as a catalyst.

Example 8 The same procedure was employed as in Example l using sodium methylate as a catalyst. The resin employed was the one described under the heading of Example 16*. This particular resin was obtained from cardanol, nonylphenol, metacresol, and formaldehyde, without the use of a catalyst. The appearance of the final product was like those in preceding examples.""

Example 9 The same procedure was employed as in Example l preceding, using sodium methylate as a catalyst. The particular resin employed was that described under the heading of Example 17. This resin was obtained from cardanol, butylphenol, metacresol, and butyraldehyde, using concentrated sulfuric acid as a catalyst. The product was similar in appearance to that obtained in previous examples. V

As to the foregoing example, and preceding examples, for further details see the table follow- Our experience with chlorinated reactants d ing oxyalkylation, particularly oxyethylation, is that an alkaline catalyst is not apt to be satisfactory if the chlorine shows any lability at all. This is usually the case, and as a result, the alkaline catalyst is converted into sodium chloride with the corresponding change in the organic reactant. In such instances we prefer to use the type of reactant employed in a Friedel-Crafts reaction. Such catalyst is an acid in some of the common systems of acid based nomenclature. Examples include aluminum chloride, ferric chloride, stannic chloride, etc. In the oxyethylation of Example 15, as described previously and described in detail inthe subsequent table, tin tetrachloride was used instead of sodium methylate. 1

The resins, prior to oxyethylation, vary from tacky resins having a suggestion of hardness,

to tacky viscous liquids. Theircolor varies from a reddish-amber to a blackish-amber, particularly in the latter direction, when the amount of cardanol or cardanol derivative increases. In the manufacture of resins, as the reaction progresses, the reaction mass frequently goes through a liquid state, to a sub-resinuous state, and then reaches the final tacky appearance, which is characteristic of these resins having a long chain substituent. As the resin is subjected to oxyethylation, these same physical changes tend to take place in reverse. If one starts with a viscous tacky resin, incipient oxyalkylation tends to make it tacky and somewhat more liquid, and further oxyalkylation makes the tackiness disappear and changes the product to a liquid. Thus, as the resin is oxyalkylated, it decreases in viscosity, i. e., becomes more liquid, or changes from a solid to a liquid, particularly when it is converted to the water-dispersible or water-soluble stage. The color of the oxyalkylated derivative is usually considerably lighter than the original product from which it is made, varying from a deep straw color to an amber or reddish-amber. The viscosity usually varies from that of an oil, like castor oil, to that of a thick, viscous syrup. Some products are waxy. The presence of a solvent, such as 15% xylene, or the like, thins the viscosity considerably and also reduces the color in dilution. No undue significance need be attached to the color, for the reason that if the same compound is prepared in glass and in iron, the latter usually has somewhat darker color. If the resins are prepared as customarily employed in varnish resin manufacture, i. e., a procedure that excludes the presence of oxygen during resinification and subsequent cooling of the resin, then, of course, the initial resin is much lighter in color. We have employed some resins which initially are almost water-white and also yield a lighter colored final product.

The same procedure as described above has 31 been applied to a large variety of resins of the kind described previously, including resins obtained from mixtures of phenols, and we have found that these oxyalkylated products having the required minimum hydrophile properties are all efiective for use in the process of the invention. In many cases resins used were obtained from aldehydes other than formaldehyde, i. e., higher aldehydes having not over 8 carbon atoms. Similarly, some of the resins, instead of being obtained by use of acid catalysts, were obtained by use of alkaline catalyst or sequential use of both types of catalysts. In some instances, the resins were obtained by a process which involved a secondary step of heating alone or under vacuum. In the series of examples represented by Examples l through 9*, the amount of a1- kylene oxide added covers the range up to about three times the weight of the initial resin. The data given in the table which follows show that many of the most effective compounds for demulsification purposes require but about onehalf this amount of alkylene oxide, in particular, ethylene oxide, for example, from 150% to possibly 200%, by weight. Larger amounts of ethylene oxide, for example, amounts up to six times the weight of the initial resin may be used, even though the solubility of such products may, in some cases, be less than the solubility of derivatives obtained with lesser amounts of alkyl-- 1 through 18 oxyethylation of a product of one of Examples The tabulated data include the example number, in which the preparation of the resin is described and the resin is identified, the amount of ethylene oxide added per weight of resin, the amount and nature of the catalyst used for the oxyethylation operations, the number of steps in which the oxyethylation was carried out, the hydrophile properties not only of the final product but also of intermediate products, the temperatures used in the oxyethylation steps, the maximum pressures (gauge) of the oxyethylation steps and the length of time required for each step. The technique used was that described in Example 1.

In the table the first column on each page gives the example number, thus identifying the resin used. Column A gives the weight of the resin solution used in grams; column B the percentage of solvent in the resin solution used; column C the percent of alkaline catalyst (sodium methylate) based on amount of resin used in the oxyethylation. Columns D1 through H5 give the data with respect to oxyethylation operations; column D1 giving the maximum temperature in degrees C; column E1 the gauge pressure in pounds per square inch; column F1 the number of grams of ethylene oxide added in the first addition; column G1 the time required for the first addition in hours; and column H1 the hydrophile properties of the product resulting from the first addition. Columns D2 through H2 give similar data for the second addition of ethylene oxide; columnsDa through H3 similar data for the third addition, etc.

Table Resin Additions oi Ethylene Oxide-First Addition Example Number A B 0 D1 E1 F1 G1 H1 43. 0 2. 3 167 160 150 2 Not emulsifiable. 39. 0 2. 0 140 170 160 1 Emulsifiable. 20.0 2.0 154 6% Insoluble. 19.9 1.4 160 100 3 Emulsifiable. 41. 0 l. 0 110 100 1% Non-emulsifiable. 55. 0 3. 1 175 195 150 $5 Do. 40. 0 2. 9 163 210 150 2% Insoluble. 40. 5 2. 6 210 150 5 Non-emulsifiable. 22.5 2.9 168 215 150 5% Insoluble. 50.0 2.9 150 34 Not emulsifiable. 39.0 2.3 170 200 150 2% Insoluble. 50.0 2.6 204 150 8 min. Not emulsifiable. 20.0 1.0 154 75 100 6% Do. 35. 0 2. 4 180 135 100 $6 Do.

1 Tin tetrachloride used as a catalyst instead of sodium methylate.

l Tin tetrachloride used as a catalyst instead of sodium methylate. 2 After 5 hours 8 grams more sodium methylate were added and run for another 5 hours, totaling 10 hours.

1 Tin tetrachloride used as a catalyst instead of sodium methylate.

Additions of Ethylene OxideFourth Addition Example Number D4 E4 F4 G4 H4 170 150 1% More soluble but still curds. 120 100 3% Almost soluble.

5 Soluble. 190 5% Emulsifiable. 190 150 1% Soluble. 220 150 1 D0. 190 150 1% Water-soluble. 230 150 2 Emulsifiable. 23-. 120 100 3% Almost watersoluble.

1 Tin tetrachloride used as a catalys ead of sodium methylate.

Table Additions oi Ethylene OxideFilth Addition Example Number Ds Es Fr GI Hi 2'. 170 195 l50 1% Not entirely soluble; uolonger curds. 7 160 120 100 3 Soluble. 15 1 150 3% Almost soluble. 23*- 160 120 100 8 Water-soluble.

1 Tin tetrachloride used as a iatalyst instead of sodium methy t In appearance the final oxyethylated products in the presence of solvent were, in general, liquids of varying viscosities and varied in color from light amber to dark brown, reddish-brown, or at times, were distinctly reddish. It will be noted that in some instances the resins contained eight moles of an anacardic acid phenol to one mole each of the other two types of phenols, i. e.,' diiunctional and trifunctional, In other instances, suitable resins might contain a single mole of an anacardic acid phenol to nine moles of a mixture having both difunctional phenols and trifunctional phenols, but, in any event, at least one mole of the nine represents the difunctional type, or one mole in nine represents the triiunctional type.

By and large, the viscosity was in the nature of castor oil or a lightly blown castor oil. Some of the products were comparatively non-viscous; others as noted, more so. In some instances, the tables themselves include reference to the viscosity of, the products, although this, of itself, is not particularly material because of the presence of asolvent. 7'

Color, in many cases, is more intimately related to the presence of a trace of iron or presence of some oxidized organic material, or even to the aldehyde used, as in the case of furfural or benzaldehyde.

The foregoing description of the appearance, viscosity, etc., of the final oxyethylated product with respect to which data are given in the table relates to the properties of the products in the presence of the solvent. It is to be understood that when these products are used for demulsification, it is unnecessary to separate them from the solvent used in their preparation, and ordinarily commercial products will, if prepared with the use of a solvent, be distributed without removal of the solvent, and frequently with the addition of other solvent materials, other agents, etc.

Actually, in considering the ratio of alkylene oxide to add, and we have previously pointed out that this can be predetermined, using laboratory tests, it is our actual preference, from a practical standpoint, to make tests on a small pilot plant scale. one run, and only one, and that we have a complete series which shows the progressive effect of introducing the oxyalkylating agent, for instance, the ethyleneoxy radicals. Our preferred procedure is as follows: We prepare a suitable resin, or for that matter, purchase it in the open market. We employ 8 pounds of resin and 4 pounds of xylene and place the resin and xylene in a suit- Our reason for so doing is that we make- 35 able autoclave with an open reflux condenser. We prefer to heat and stir until the solution is complete.

We have pointed out that the resins obtained from cardanol, cardanol derivatives, or these same phenols, in combination with other phenol, such as metacresol or para-amylphenol, or both metacresol and para-amylphenol, are apt to yield soft resins or viscous tacky fluids. If such resins are used, a solvent need not be added, but may be added as a matter of convenience, or for comparison, if desired. We then add a catalyst, for instance, 2% of caustic soda, in the form of a to 30% solution, and remove the water of solution or formation. Attention is directed to what has been said previously about replacing 2% of an alkaline catalyst, such as caustic soda or sodium methylate, with about l /2%, or thereabouts, of a metallic chloride, such as tin tetrachloride. We then shut off the reflux condenser and use the equipment as an autoclave only, and oxyethylate until a total of 60 pounds of ethylene oxide has been added equivalent to 750% of the original resin. We prefer a temperature of about 150 C. to 175 C. We also take samples at interinediate points, as indicated in the following able:

Oxyethylation to 750% can usually be completed within 30 hours and frequently more quickly.

The samples taken are rather small, for instance, 2 to 4 inches, so that no correction need be made in regard to the residual reaction mass. Each sample is divided in two. One-half the sample is placed in an evaporating dish on the steam bath overnight so as to eliminate the xylene. Then 1.5% solutions are prepared from both series of samples, 1. e., the series with xylene present and the series with xylene removed.

Mere visual examination of any samples in solution may be sufiicient to indicate hydrophile character or surface activity, i. e., the product is soluble, forming a colloidal sol, or the aqueous solution foams or shows emulsifying property. All these properties are related through adsorption at the interface, for example, a gas-liquid interface or a liquid-liquid interface. If desired, surface-activity can be measured in any one of the usual ways, using a Du Nouy tensiometer or dropping pipette, or any other procedure for measuring interfacial tension. Any compound having sub-surface-activity, and all derived from the same resin and oxyalkylated to a greater extent, i. e., those having a greater proportion of alkylene oxide, are useful for the practice of this invention.

We have previously pointed out that when cardanol or cardanol derivatives of the kind herein described are used, either alone or in conjunction with a difunctional phenol, one could add a substantial amount of a trifunctional 36 phenol, such as hydroxy benzene or metacresol, as described and illustrated by numerous examples. Needless to say, if one obtains an insoluble, infusible resin, from hydroxy benzene or metacresol the mere addition of a small amount of a cardanol derivative along with a small amount of a difunctional phenol will not render the resin of such mixture soluble and fusible if the usual procedure is employed. For this reason, we prefer a pilot plant test of the kind abovedescribed, because we can use the same procedure to evaluate the acceptability of a mixture containing a trifunctional phenol, such as hydroxy benzene or metacresol along with cardanol or a cardanol derivative in conjunction with a difunctional phenol. This is the same sort of a procedure that one would employ to evaluate the tolerance of a resin made solely from a difunctional phenol, such as para-amylphenol, towards the presence of a trifunctional phenol. Previous reference has been made to the fact that one can conduct a laboratory scale test which will indicate whether or not a resin, although soluble in a solvent, will yield an insoluble rubbery product, i. e., a product which is neither hydrophile nor surface-active u on oxyalk lation, particularly extensive Oxyethylation. It is also obvious that one may have a solvent-soluble resin which will result in an insoluble rubber at the ultimate stages of Oxyethylation but not at the earlier stages. In other words, resinsfrom such phenols, and at times, resins obtained from chlorinated cardanol, show thi character tic. The addition of 2 or 3 moles of the oxyalkylatine; agent per phenolic nucleus, particularly ethylene oxide, gives a surface-active product which is erf ctly sati factory, while more extensive Oxyethylation yields an insoluble rubber, i. e., an unsuitable product. It is obv ous that thi pre ent procedure of evaluat n trifunctional phenol tol rance is mo e suitable than the re ious procedure.

It may be well to call attention to one result which may be noted in a lon drawn-out oxyalkvlation, particularly oxy thylation, which would not appear in a normally conducted reaction. Reference has been made to cross-linking and its effect on solubility and also the fact that, if carried far enough, it causes incipient stringiness, then pronounced stringiness, usua ly follo ed by a semi-rubbery or rubbery stage. Incipient stringiness, or even pronounced stringiness, or even the tendency towards a rubbery stage. is not objectionable, so long as the final product is still hydro i e and at least suh-surface-active. Such materials are frequently best mixed with a polar solvent, such as alcohol or the like, and pref rably an alcoholic solution is used. The point which we want to make, however, is this: Strin iness or rubberization at this stage may possibly be the result of etherification. Obviously, if a suitable phenol and an aldehyde produce a noncross-linked resin molecule, and if such molecule is oxyalkylated so as to introduce a plurality of hydroxyl groups in each molecule, then and in that event, if subsequent etherification takes place, one is going to obtain crosslinking in the same general way that one would obtain crosslinking in other resinification reactions. Ordinarily, there is little or no tendency towards etherification during the oxyalkylation step. If it does take place at all, it is only to an insignificant and undetectable degree. However, suppose that a certain weight of resin is treated with an equal weight of, or twice its weight of, ethylene oxide m y be done in a comparatively 37 short time, for instance, 'at 150 to 175 C. in 4 to 8 hours, or even less. I On the other hand, if in an exploratory reaction, such as the kind previously described, the ethylene oxide were added extremely slowly in order to take stepwise samples, so that the reaction required 4 or times as long to introduce an equal amount of ethylene oxide employing the same temperature, then etherification might cause stringiness or a suggestion of rubberiness. For this reason if in an exploratory experiment of the kind previously described there appears to be any stringiness or rubberiness, it may be well to repeat the experiment and reach the intermediate stage of oxyalkylation as rapidly as possible and then proceed slowly beyond this intermediate stage. The entire purpose of this modified procedure is to cut down the time of reaction so as to avoid etherification if it be caused by the extended time-period.

It may be well to note one peculiar reaction sometimes noted in the course of oxyalkylation, particularly oxyethylation, of the thermoplastic resins herein described. This effect is noted in a case where a thermoplastic resin has been oxyalkylated, for instance, oxyethylated, until it gives a perfectly clear solution, even in the presence of some accompanying water-insoluble solvent such as 10% to of xylene. Further oxyalkylation, particularly oxyethylation, may

then yield a product which, instead of giving a produced, indicated thus:

Ha Qowunomn C so H(i lH I 0 Oommon. 02

This fact, of course, presents no difficulty for the reason that oxyalkylation can be conducted .in each instance stepwise, or at a gradual rate, and samples taken at short intervals so as to arrive at a point where optimum surface activity or hydrophile character is obtained if desired; for products for use in the practice of this invention, this is not necessary'and, in fact, may be undesirable, i. e., reduce the efiiciency of the product.

We do not know to what extent oxyalkylation produces uniform distribution in regard to phenolic hydroxyls present in the resin molecule. In some instances, of course, such distribution can not be uniform for the reason that we have not specified that the molecules of ethylene oxide, for example, be added in multiples of the units present in the resin molecule. This may be illustrated in the following manner:

Suppose the resin happens to have five phenolic nuclei. If a minimum of two moles of ethylene oxide per phenolic nucleus are added, this would oxide, or 12, or 13, or 14 moles; obviously, even mean an addition of 10 moles of ethylene oxide but suppose that one added 11 moles of ethylene one mole of the same aldehyde under conditions assuming the most uniform distribution possible, some of the polyethyleneoxy radicals would contain 3 ethyleneoxy units and some would contain 2. Therefore, it is impossible to specify uniform distribution in regard to the entrance of the ethylene oxide or other oxyalkylating agent. For that matter, if one were to introduce 25 moles of ethylene oxide there is no way to be certain that all chains would have 5 units; there might be some having, for example, 4 and 6 units, or for that matter 3 or 7 units. Nor is there any basis for assuming that the number of molecules of-the oxyalkylating agent added to each of the molecules of the resin is the same, or difierent. Thus, where formulae are given to illustrate or depict the oxyalkylated products, distributions of radicals indicated are to be statistically taken. We have, however, included specific directions and specifications in regard to the total amount of ethylene oxide, or total amount of any other oxyalkylating agent, to add.

In regard to solubility of the resins and the oxyalkylated compounds, and for that matter deriva tives of the latter, the following should be noted. In oxyalkylation, any solvent employed should be non-reactive to the alkylene oxide employed. This limitation does not apply to solvents used in cryoscopic determinations for obvious reasons. Attention is directed to the fact that various organic solvents may be employed to verify that the resin is organic solvent-soluble. Such solubility test merely characterizes the resin. The particular solvent used in such test may not be suitable for a molecular weight determination and, likewise, the solvent used in determining molecular weight may not be suitable as a solvent during oxya kylation. For solution of the oxyalkylated compounds, or their derivatives, a great variety of solvents may be employed, such as alcohols, ether alcohols, cresols, phenols, ketones, esters, etc., alone or with the addition of water. Some of these are mentioned hereafter. We prefer the use of benzene or diphenylamine as a solvent in making cryoscopic measurements. The most satisfactory resins are those which are soluble in xylene or the like, rather than those which are soluble only in some other solvent containing elements other than carbon and hydrogen, for instance, oxygen or ch orine. Such solvents are usually polar, semi-polar, or slightly polar in nature compared with xylene, cymene, etc.

Reference to cryosconic measurement is concerned with the use of benzene or other suitable compound as a solvent. Such method will show that conventional resins obtained, for example, from para-tertiar amylphenol and formaldehyde in presence of an acid catalyst, will have a molecular weight indicating 3, 4. 5 or somewhat greater number of structural units per molecule. If more drastic conditions of resinification are employed or if such low-stage resin is subjected to a vac uum distillation treatment as previously de scribed, one obtains a resin of a distinctly higher molecular weight. Any molecular weight determination used, whether cryoscopic measurement or otherwise, other than the conventional cryoscopic one employing benzene, should be checked so as to insure that it gives consistent values on such conventional resins as a control. Frequently all that is necesary to make an approximation of the molecular weight range is to make a comparison with the dimer obtained by chemical combination of two moles of the same phenol, and

r r 39 to insure dimerization. As to the preparation of dimers from substituted phenols, see Carswell, Phenoplasts, page 31. The increased viscosity, resinous character, and decreased solubility, etc., of the higher polymers in comparison with the dimer, frequently are all that is required to establish that the resin contains 3 or more structural units per molecule.

Conventional demulsifying agents employed in the treatment of oil field emulsions are used as such, or after dilution with any suitable solvent.

such as water, petroleum hydrocarbons, such as benzene, toluene, xylene, tar acid oil, cresol, anthracene oil, etc. Alcohols, particularly aliphatic alcohols, such as methyl alcohol, ethyl alcohol, denatured alcohol, propyl alcohol, butyl alcohol, hexyl alcohol, octyl alcohol, etc., may be employed as diluents. Miscellaneous solvents such as pine oil, carbon tetrachloride, sulfur dioxide extract obtained in the refining of petroleum, etc., may be employed as diluents. Similarly, the material or materials employed as the demulsifying agent of our process may be admixed with one or more of the solvents customarily used in connection with conventional demulsifying agents. Moreover, said material or materials may be used alone or in admixture with other suitable well-known classes of demulsifying agents.

It is well known that conventional demulsifying agents may be used in a water-soluble form, or in an oil-soluble form, or in a form exhibiting both oiland water-solubility. Sometimes they may be used in a form which exhibits relatively limited oil solubility. However, since such reagents are frequently used in a ratio of l to 10,000, or 1 to 20,000, or 1 to 30,000, or even 1 to 40,000, or 1 to 50,000, as in desalting practice, such an apparent insolubility in oil and water is not significant because said reagents undoubtedly have solubility within such concentrations. This same fact is true in regard to the material or materials employed as the demulsifying agent of our process.

The present invention is concerned with treatment of petroleum emulsions by means of certain oxyalkylated resins which are hydrophile or subsurfaceor surface-active. Such resins, in turn, are oxyalkylation-susceptible, water-insoluble, organic solvent-soluble, fusible, phenoLaldehyde resins, derived from difunctional phenols having a 2,4,6 hydrocarbon substituent with 4 to 8 carbon atoms. Based on actual large scale application in a large number of oil fields in the United States and certain foreign countries, we believe that this type of material, the oxyalkylated products of fusible solvent-soluble resins, particularly phenol-aldehyde resins, either as such or in the form of derivatives, ultimately will be employed in no less than 50% of all chemical demulsifying agents used throughout the world.

We have employed oxyalkylated cardanol resins of the kind herein described and in numerous instances have resolved the emulsion, using 25 parts per million, or less, of the demulsifying agent. In actual commercial use, of course, the use of cardanol resins depends upon whether or not phenol is obtained as economically or more economically than some other competitive phenol, such as para-amylphenol, para-butylphenol, etc.

In practising our process for resolving petroleum emulsions of the water-in-oil type, a treating agent or demusifying agent of the kind above described is brought into contact with or caused to act upon the emulsion to be treated, in any of the various apparatus now generally used to resolve or break petroleum emulsions with a chemical reagent, the above procedure being used alone or in combination with other demulsifying procedure, such as the electrical dehydration process.

One type of procedure is to accumulate a volume of emulsified oil in a tank and conduct a batch treatment type of demulsification procedure to recover clean oil. In this procedure the emulsion is admixed with the demulsifier, for example by agitating the tank of emulsion and slowly dripping demulsifier into the emulsion. In some cases mixing is achieved by heating the emulsion while dripping in the demulsifier, depending upon the convection currents in the emulsion to produce satisfactory admixture. In a third modification of this type of treatment, a circulating pump withdraws emulsion from, e. g., the bottom of the tank, and re-introduces it into the top of the tank, the demulsifier being added, for example, at the suction side of said circulating P p.

In a second type of treating procedure, the demulsifier is introduced into the well fluids at the well-head or at some point between the wellhead and the final oil storage tank, by means of an adjustable proportioning mechanism or proportioning pump. Ordinarily the flow of fiuids through the subsequent lines and fittings sufiices to produce the desired degree of mixing of demulsifier and emulsion, although in some instances additional mixing devices may be introduced into the flow system. In this general procedure, the system may include various mechanical devices for withdrawing free water, separating entrained water, or accomplishing quiescent settling of the chemicalized emulsion. Heating devices may likewise be incorporated in any of the treating procedures described herein.

A third type of application (down-the-hole) of demulsifier to emulsion is to introduce the demulsifier either periodically or continuously in di'uted or undiluted form into the well and to allow it to come to the surface with the well fluids, and then to flow the chemicalized emulsion through any desirable surface equipment, such as employed in the other treating procedures. This particular type of application is decidedly useful when the demulsifier is used in connection with acidifiction of calcareous oil-bearing strata, especially if suspended in or dissolved in the acid employed for acidification.

In all cases, it will be apparent from the foregoing descriotion, the broad process consists simply in introducing a relatively small proportion of demulsifier into a relatively large proportion of emulsion, admixing the chemical and emulsion either throrgh natural flow or through special apparatus, with or without the application of heat, and allowing the mixture to stand quiescent until the undesirable water content of the emulsion separates and settles from the mass.

The following is a typical instal ation:

A reservoir to hold the demulsifier of the kind described (diluted or undiluted) is placed at the well-head where the eflluent liquids leave the well. This reservoir or container, which may vary from 5 ga'lons to gallons for convenience, is connected to a proportioning pump which injects the demulsifier drop-wise into the fluids leaving the well. Such chemicalized fluids pass through the fiowline into a settling tank. The settling" tank consists of a tank of any convenient size, for instance, one which will hold amounts of fluid produced in 4 to 24 hours (500 barrels to 2000 

1. A PROCESS FOR BREAKING PETROLEUM EMULSIONS OF THE WATER-IN-OIL TYPE, CHARACTERIZED BY SUBJECTING THE EMULSION TO THE ACTION OF A DEMULSIFYING AGENT INCLUDING HYDROPHILE SYNTHETIC PRODUCTS; SAID HYDROPHILE SYNTHETIC PRODUCTS BEING OXYALKYLATION PRODUCTS OF (A) AN ALPHA-BETA ALKYLENE OXIDE HAVING NOT MORE THAN 4 CARBON ATOMS AND SELECTED FROM THE CLASS CONSISTING OF ETHYLENE OXIDE, PROPYLENE OXIDE, BUTYLENE OXIDE, GLYCIDE AND METHYLGLYCIDE, AND (B) AN OXYALKYLATION-SUSCEPTIBLE, FUSIBLE, ORGANIC SOLVENT-SOLUBLE, WATER-INSOLUBLE PHENOL-ALDEHYDE RESIN; SAID RESIN BEING DERIVED BY REACTION BETWEEN A REACTANT CONSISTING OF A MIXTURE OF AN ANACARDIC ACID PHENOL, A DIFUNCTIONAL PHENOL, AND A TRIFUNCTIONAL PHENOL ON THE ONE HAND, THE MIXTURE CONTAINING AT LEAST ONE MOLE OF ANACARDIC ACID PHENOL FOR EACH 10 MOLES OF TOTAL PHENOL AND THE ANACARDIC ACID PHENOL AND DIFUNCTIONAL PHENOL CONSTITUTING THE MAJOR PROPORTION OF THE PHENOL MIXTURE, AND ON THE OTHER HAND AN ALDEHYDE HAVING NOT OVER 8 CARBON ATOMS AND REACTIVE TOWARD SAID PHENOLIC REACTANT; SAID OXYALKYLATED RESIN BEING CHARACTERIZED BY THE INTRODUCTION INTO THE RESIN MOLECULE OF A PLURALITY OF DIVALENT RADICALS HAVING THE FORMULA (R1O)N, IN WHICH R1 IS A MEMBER SELECTED FROM THE CLASS CONSISTING OF ETHYLENE RADICALS, PROPYLENE RADICALS, BUTYLENE RADICALS, HYDROXY PROPYLENE RADICALS, AND N IS A NUMERAL VARYING FROM 1 TO 20; WITH THE PROVISO THAT AT LEAST 2 MOLES OF ALKYLENE OXIDE BE INTRODUCED FOR EACH PHENOLIC NUCLEUS; SAID ANACARDIC PHENOLIC CONSTITUENT BEING DERIVED FROM THE CLASS CONSISTING OF AN ANACARDIC ACID PHENOL AND A SIDE CHAIN CHLORINATED AND A SIDE CHAIN HYDROGENATED DERIVATIVE THEREOF. 